Ultrasensitive, visible tunable diode laser detection of NO(2)

Recent advances in room-temperature visible diode lasers and ultrasensitive detection techniques have been exploited to create a highly sensitive tunable diode laser absorption technique for in situ monitoring of NO(2) in the lower troposphere. High sensitivity to NO(2) is achieved by probing the visible absorption band of NO(2) with an AlGalnP diode laser at 640 or 670 nm combined with a balanced ratiometric electronic detection technique. We have demonstrated a sensitivity of 3.5 × 10(10) cm(-3) for neat NO(2) in a 1-m path at 640 nm and have estimated a sensitivity for ambient operation of 5 ppbv m (l0 ppbv m at 670 nm), where ppbvm is parts in 10(9) by volume per meter of absorption path length, from measured pressure-broadening coefficients.     

High-sensitivity instrument for measuring atmospheric NO2

We report on the development of a high-sensitivity detection system for measuring atmospheric NO2 using a laser-induced fluorescence (LIF) technique around 440 nm. A tunable broad-band optical parametric oscillator laser pumped by the third harmonic of a Nd:YAG laser is used as a fluorescence excitation source. The laser wavelength is tuned at peak and bottom wavelengths around 440 nm alternatively, and the difference signal at the two wavelengths is used to extract the NO2 concentration. This procedure can give a good selectivity for NO2 and avoid interferences of fluorescent or particulate species other than NO2 in the sample air. The NO2 instrument developed has a sensitivity of 30 pptv in 10 s and S/N = 2. The practical performance of the detection system is tested in the suburban area for 24 h. The intercomparisons between the LIF instrument and a photofragmentation chemiluminescence (PF-CL) instrument have been performed under laboratory conditions. The correlation between the two instruments is measured up to 1000 pptv. A good linear relationship between the LIF measurements and the PF-CL measurements is obtained.     

Development of a photofragmentation laser-induced-fluorescence laser sensor for detection of 2, 4, 6-trinitrotoluene in soil and groundwater

Laser photofragmentation (PF) and subsequent nitric oxide (NO) laser-induced fluorescence (LIF) have been developed to measure the concentration of energetic materials (EM's), such as 2, 4, 6-trinitrotoluene (TNT), in soil and other media. Gas-phase EM's photodissociate, releasing NO(2), when exposed to laser radiation near 226 nm. Laser-excited NO(2) predissociates to form NO that gives an intense fluorescence when excited near 226 nm. The EM concentration is inferred from the intensity of the NO fluorescence. A PF-LIF laser-based sensor is being developed to be used with the U.S. Army Corps of Engineers' Waterways Experiment Station's cone penetrometer to measure in situ the concentration of subsurface TNT. Several factors that affect the PF-LIF signal waveforms, such as sample temperature, laser power, and heating time, were investigated. Also, effects on the PF-LIF signal of adding water and fertilizer to the TNT mixtures were studied. Decay times were determined by least-squares fitting of the exponential PF-LIF signal waveforms. The use of PF-LIF waveforms promises to enable diagnostics of the sample's characteristics that would otherwise not be possible in situ.     

Laser-induced fluorescence detection of atmospheric NO2 with a commercial diode laser and a supersonic expansion

Routine observations of atmospheric NO2 at concentrations ranging from 0.1 to 100 parts per billion are needed for air quality monitoring and for the evaluation of photochemical models. We have designed, constructed, and field tested a relatively inexpensive and specific NO2 sensor using laser-induced fluorescence. The instrument combines a commercial cw external-cavity tunable diode laser (640 nm) and a continuous supersonic expansion. The total package is completely automated, has a modest size of 0.5 m3 and 118 kg, and could be manufactured at competitive price, with the current generation of instruments. The sensitivity of the instrument is 145 part per trillion by volume min(-1) (signal-to-noise ratio of 2), which is more than adequate for monitoring purposes.     

On-line multicomponent trace-gas analysis with a broadly tunable pulsed difference-frequency laser spectrometer

The design and application of a novel automated room-temperature laser spectrometer are reported. The compact instrument is based on difference-frequency generation in bulk LiNbO(3). The instrument employs a tunable cw external-cavity diode laser (795-825 nm) and a pulsed diode-pumped Nd:YAG laser (1064 nm). The generated mid-IR nanosecond pulses of 50-muW peak power and 6.5-kHz repetition rate, continuously tunable from 3.16 to 3.67 mum, are coupled into a 36-m multipass cell for spectroscopic studies. On-line measurements of methane are performed at concentrations between 200 ppb (parts in 10(9) by mole fraction) and approximately 1%, demonstrating a large dynamic range of 7 orders of magnitude. Furthermore computer-controlled multicomponent analysis of a mixture containing five trace gases and water vapor with an overall response time of 90 s at an averaging time of only approximately 30 s is reported. A minimum detectable absorption coefficient of 1.1 x 10(-7) cm(-1) has been achieved in an averaging time of 60 s, enabling detection limits in the ppb range for many important trace gases, such as CH(4), C(2)H(6), H(2)CO, NO(2), N(2)O, HCl, HBr, CO, and OCS.     

A compact diode laser cavity ring-down spectrometer for atmospheric measurements of NO3 and N2O5 with automated zeroing and calibration

A compact rack-mounted cavity ring-down spectrometer (CRDS) for simultaneous measurements of the nocturnal nitrogen oxides NO(3) and N(2)O(5) in ambient air is described. The instrument uses a red diode laser to quantify mixing ratios of NO(3) (at its absorption maximum at 662 nm) and of N(2)O(5) following its thermal dissociation to NO(3) in a second detection channel. The spectrometer is equipped with an automated zeroing and calibration setup to determine effective NO(3) absorption cross-sections and NO(3) and N(2)O(5) inlet transmission efficiencies. The instrument response was calibrated using simultaneous measurements of NO(2), generated by thermal dissociation of N(2)O(5) and/or by titration of NO(3) with excess NO, using blue diode laser CRDS at 405 nm. When measuring ambient air, the (2σ, 10 s) precision of the red diode CRDS varied between 5 and 8 parts-per-trillion by volume (pptv), which sufficed to quantify N(2)O(5) concentrations under moderately polluted conditions. Sample N(2)O(5) measurements made on a rooftop on the University of Calgary campus in August 2010 are presented. A maximum N(2)O(5) mixing ratio of 130 pptv was observed, corresponding to a steady-state lifetime of less than 50 min. The NO(3) mixing ratios were below the detection limit, consistent with their predicted values based on equilibrium calculations. During the measurement period, the instrument response for N(2)O(5) was 70% of the theoretical maximum, rationalized by a slight mismatch of the laser diode output with the NO(3) absorption line and a N(2)O(5) inlet transmission efficiency less than unity. Advantages and limitations of the instrument's compact design are discussed.     

Investigation of optical fibers for gas-phase, ultraviolet laser-induced-fluorescence (UV-LIF) spectroscopy

We investigate the feasibility of transmitting high-power, ultraviolet (UV) laser pulses through long optical fibers for laser-induced-fluorescence (LIF) spectroscopy of the hydroxyl radical (OH) and nitric oxide (NO) in reacting and non-reacting flows. The fundamental transmission characteristics of nanosecond (ns)-duration laser pulses are studied at wavelengths of 283 nm (OH excitation) and 226 nm (NO excitation) for state-of-the-art, commercial UV-grade fibers. It is verified experimentally that selected fibers are capable of transmitting sufficient UV pulse energy for single-laser-shot LIF measurements. The homogeneous output-beam profile resulting from propagation through a long multimode fiber is ideal for two-dimensional planar-LIF (PLIF) imaging. A fiber-coupled UV-LIF system employing a 6 m long launch fiber is developed for probing OH and NO. Single-laser-shot OH- and NO-PLIF images are obtained in a premixed flame and in a room-temperature NO-seeded N(2) jet, respectively. Effects on LIF excitation lineshapes resulting from delivering intense UV laser pulses through long fibers are also investigated. Proof-of-concept measurements demonstrated in the current work show significant promise for fiber-coupled UV-LIF spectroscopy in harsh diagnostic environments such as gas-turbine test beds.     

Laser photofragmentation-fragment detection and pyrolysis-laser-induced fluorescence studies on energetic materials

Trace concentrations of energetic materials such as 2, 4, 6-trinitrotoluene (TNT), pentaerythritol tetranitrate (PETN), and hexahydro-1, 3, 5-trinitro-s-triazine (RDX) are detected by laser photofragmentation-fragment detection (PF-FD) spectrometry. In this technique, a single laser operating near 227 nm photofragments the parent molecule and facilitates the detection of the characteristic NO fragment by means of its A (2)Sigma(+)-X (2)Sigma (0, 0) transitions near 227 nm. Fragment detection is accomplished by resonance-enhanced multiphoton ionization with miniature electrodes and by laser-induced fluorescence (LIF) with a photodetector. Experiments are also conducted in the visible region by use of 453.85-nm radiation for photofragmentation and fragment detection. Sand samples contaminated with PETN and RDX are analyzed by a pyrolysis-LIF technique, which involves pyrolysis of the energetic material with subsequent detection of the pyrolysis products NO and NO(2) by LIF and PF-LIF, respectively, near 227 nm. The application of these techniques to the trace analysis of TNT, PETN, and RDX at ambient pressure in room air is demonstrated with limits of detection (signal-to-noise ratio, 3) in the low parts-in-10(9) to parts-in-10(6) range for a 20-s integration time and 10-120 microJ of laser energy at 226.8 nm and approximately 5 mJ at 453.85 nm. An increase in detection sensitivity is projected with an increase in laser energy and an improved system design. The analytical merits of these techniques are discussed and compared with those of other laser-based techniques.     

Strategies for laser-induced fluorescence detection of nitric oxide in high-pressure flames. I. A-X(0,0) excitation

Three different high-pressure flame measurement strategies for NO laser-induced fluorescence (LIF) with A-X(0,0) excitation have been studied previously with computational simulations and experiments in flames up to 15 bars. Interference from O2 LIF is a significant problem in lean flames for NO LIF measurements, and pressure broadening and quenching lead to increased interference with increased pressure. We investigate the NO LIF signal strength, interference by hot molecular oxygen, and temperature dependence of the three previous schemes and for two newly chosen excitation schemes with wavelength-resolved LIF measurements in premixed methane and air flames at pressures between 1 and 60 bars and a range of fuel/air ratios. In slightly lean flames with an equivalence ratio of 0.83 at 60 bars, the contribution of O2 LIF to the NO LIF signal varies between 8% and 29% for the previous schemes. The O2 interference is best suppressed with excitation at 226.03 nm.     

Luminol/H2O2 chemiluminescence detector for the analysis of nitric oxide in exhaled breath

A new instrument for the detection of nitric oxide has been developed and applied to the analysis of exhaled breath. The instrument is based on conversion of NO to NO2, using the oxidant chromium trioxide, followed by detection of chemiluminescence in the reaction of NO2 with an alkaline luminol/H2O2 solution. The presence of H2O2 is found to enhance the sensitivity of NO2 detection by a factor of approximately 20. A bundle of porous polypropylene hollow fiber membranes is used to bring the gaseous sample into contact with the luminol solution. Chemiluminescence occurring within the translucent hollow fibers is detected using a miniature photomultiplier tube. The limit of detection for NO is 0.3 ppbv for S/N = 3, and the 1/e response time is 2 s. A large interference resulting from the 4-6% CO2 concentration in exhaled breath is removed by use of an ascarite scrubber in the air stream. Breath measurements of NO were made using a sampling technique developed by Sensor Medics (Yorba Linda, CA) with simultaneous detection using the luminol/H2O2 and NO + O3 chemiluminescence techniques. The two instruments were found to be in excellent agreement. Nitric oxide levels were in the range 6.0-22.0 ppbv for healthy individuals and 40.0-80.0 ppbv for individuals with asthma or a respiratory infection. This new detector offers the advantages of compact size, low cost, and a simple configuration compared to NO detectors based on NO + O3 chemiluminescence.     

Mid-infrared quantum cascade laser based off-axis integrated cavity output spectroscopy for biogenic nitric oxide detection

Tunable-laser absorption spectroscopy in the mid-IR spectral region is a sensitive analytical technique for trace-gas quantification. The detection of nitric oxide (NO) in exhaled breath is of particular interest in the diagnosis of lower-airway inflammation associated with a number of lung diseases and illnesses. A gas analyzer based on a continuous-wave mid-IR quantum cascade laser operating at approximately 5.2 microm and on off-axis integrated cavity output spectroscopy (ICOS) has been developed to measure NO concentrations in human breath. A compact sample cell, 5.3 cm in length and with a volume of < 80 cm3, that is suitable for on-line and off-line measurements during a single breath cycle, has been designed and tested. A noise-equivalent (signal-to-noise ratio of 1) sensitivity of 10 parts in 10(9) by volume (ppbv) of NO was achieved. The combination of ICOS with wavelength modulation resulted in a 2-ppbv noise-equivalent sensitivity. The total data acquisition and averaging time was 15 s in both cases. The feasibility of detecting NO in expired human breath as a potential noninvasive medical diagnostic tool is discussed.     

Ammonia detection by using quantum-cascade laser photoacoustic spectroscopy

A pulsed quantum-cascade distributed-feedback laser, temperature tunable from -41 degrees C to +31.6 degrees C, and a resonant differential photoacoustic detector are used to measure trace-gas concentrations to as low as 66 parts per 10(9) by volume (ppbv) ammonia at a low laser power of 2 mW. Good agreement between the experimental spectrum and the simulated HITRAN spectrum of NH3 is found in the spectral range between 1046 and 1052 cm(-1). A detection limit of 30 ppbv ammonia at a signal-to-noise ratio of 1 was obtained with the quantum-cascade laser (QCL) photoacoustic (PA) setup. Concentration changes of approximately 50 ppbv were detectable with this compact and versatile QCL-based PA detection system. The performance of the PA detector, characterized by the product of the incident laser power and the minimum detectable absorption coefficient, was 4.7 x 10-9 W cm(-1).     

Two-photon nitric oxide laser-induced fluorescence measurements in a diesel engine

A two-photon nitric oxide (NO) laser-induced fluorescence (LIF) technique was developed and applied to study in-cylinder diesel combustion. The technique prevents many problems associated with in-cylinder, single-photon NO planar-laser-induced fluorescence measurements, including fluorescence interference from the Schumann-Runge bands of hot O2, absorption of a UV excitation beam by in-cylinder gases, and difficulty in rejecting scattered laser light while simultaneously attempting to maximize fluorescence signal collection. Verification that the signal resulted from NO was provided by tuning of the laser to a vibrational off-resonance wavelength that showed near-zero signal levels, which resulted from either fluorescence or interference at in-cylinder pressures of as much as 20 bar. The two-photon NO LIF signal showed good qualitative agreement with NO exhaust-gas measurements obtained over a wide range of engine loads.     

二氧化氮差分吸收激光雷达拉曼激光源的优化研究

Nd:YAG三倍频激光(355nm)抽运高压CH4,获得其第一级斯托克斯光S1(395.60nm),作为NO2差分吸收激光雷达(NO2-DIAL)的激光源λon.通过增大激光脉冲宽度、改变拉曼池耦合透镜的焦距和气体压强等条件,获得了满足实际使用要求的转化效率高、稳定性好的395.60nm波长拉曼激光输出.该实验结果已应用于差分吸收激光雷达的NO2探测.     

Development of a selective light-emitting diode photolytic NO(2) converter for continuously measuring NO(2) in the atmosphere

A photolytic converter of nitrogen dioxide (NO(2)) to nitric oxide (NO) using light-emitting diodes (LEDs) has been designed to measure NO(2) in the troposphere. The typical electrical power consumption of the photolytic converter (PLC) is only 44 W. The maximum conversion efficiency of NO(2) to NO of the photolytic converter is around 90%, which is higher than that of metal halides or high-pressure Xe arc lamps (up to ～70%). The conversion efficiency of the PLC was almost constant for at least 2.5 months. The conversion efficiency of peroxyacetyl nitrate by the LED-PLC was measured to be 2.6 ± 0.1% (1σ). The interference of HONO using the PLC was experimentally estimated to be less than 3%, which is within the uncertainty of the instrument. An intercomparison of NO(2) measurements between the PLC-CLD and the laser-induced fluorescence (LIF) technique was conducted, and the NO(2) concentrations measured by the PLC-CLD method were in agreement with those obtained by the LIF technique, within the uncertainties of the instruments. Continuous observations were made on Fukue Island, a remote area. These results demonstrate the performance of the PLC for continuous ambient measurements.     

Comparisons of laser-saturated, laser-induced, and planar laser-induced fluorescence measurements of nitric oxide in a lean direct-injection spray flame

We report quantitative, spatially resolved laser-saturated fluorescence (LSF), linear laser-induced fluorescence (LIF), and planar laser-induced fluorescence (PLIF) measurements of nitric oxide (NO) concentration in a preheated, lean direct-injection spray flame at atmospheric pressure. The spray is produced by a hollow-cone, pressure-atomized nozzle supplied with liquid heptane, and the overall equivalence ratio is unity. NO is excited by means of the Q(2)(26.5) transition of the gamma(0, 0) band. LSF and LIF detection are performed in a 2-nm region centered on the gamma(0, 1) band. PLIF detection is performed in a broad ~70-nm region with a peak transmission at 270 nm. Quantitative radial NO profiles obtained by LSF are presented and analyzed so as to correct similar LIF and PLIF profiles. Excellent agreement is achieved among the three fluorescence methodologies.     

Strategies for laser-induced fluorescence detection of nitric oxide in high-pressure flames. III. Comparison of A-X excitation schemes

Laser-induced fluorescence (LIF) has proven a reliable technique for nitric oxide (NO) diagnostics in practical combustion systems. However, a wide variety of different excitation and detection strategies are proposed in the literature without giving clear guidelines of which strategies to use for a particular diagnostic situation. We give a brief review of the high-pressure NO LIF diagnostics literature and compare strategies for exciting selected transitions in the A-X(0, 0), (0, 1), and (0, 2) bands using a different detection bandpass. The strategies are compared in terms of NO LIF signal strength, attenuation of laser and signal light in the hot combustion gases, signal selectivity against LIF interference from O2 and CO2, and temperature and pressure sensitivity of the LIF signal. The discussion is based on spectroscopic measurements in laminar premixed methane-air flames at pressures between 1 and 60 bars and on NO and O2 LIF spectral simulations.     

A REMPI method for the ultrasensitive detection of NO and NO2 using atmospheric pressure laser ionization mass spectrometry

We report on the development of a quasi-simultaneous highly selective method for NO and NO2 detection at the ultratrace level. Atmospheric pressure laser ionization (APLI), recently introduced by our group, is used to detect both compounds at low parts per trillion by volume (pptv) mixing ratios. APLI is based on resonance-enhanced multiphoton ionization mass spectrometry. Two-color pump-probe experiments employing a single excimer pumped dye laser combination allow for the ultrasensitive measurement of NO and NO2 within a narrow range of maximum pumping efficiency of the laser dye Coumarin 120. NO is detected via excitation of the long-lived A 2sigma+ (nu' = 1) level at 215.36 nm and subsequently ionized with 308-nm radiation provided by the excimer pump laser. NO2 is ionized after double resonant excitation of the A2B1 and 3psigma manifolds in a (1 + 1' + 1(')) process using 431.65 + 308 nm. The selectivity of the NO measurement exceeds 2,000 with respect to NO2 and N2O5. For NO2, a selectivity of >3,000 with respect to N2O5 and organic nitrates is observed. The current APLI detection limit of NO and NO2 is 0.5 and 5 pptv, respectively, with a 20-s integration time.     

Intracavity CO laser photoacoustic trace gas detection: cyclic CH(4), H(2)O and CO(2) emission by cockroaches and scarab beetles

A liquid-nitrogen-cooled CO laser and an intracavity resonant photoacoustic cell are employed to monitor trace gases. The setup was designed to monitor trace gas emissions of biological samples on line. The arrangement offers the possibility to measure gases at the 10(9) by volume (ppbv) level (e.g., CH(4), H(2) O) and to detect rapid changes in trace gas emission. A detection limit of 1 ppbv for CH(4) in N(2) equivalent to a minimal detectable absorption of 3 × 10(-9) cm(-1) can be achieved. Because of the kinetic cooling effect we lowered the detection limit for CH(4) in air is decreased to 10 ppbv. We used the instrument in a first application to measure the CH(4) and H(2) O emission of individual cockroaches and scarab beetles. These emissions could be correlated with CO(2) emissions that were recorded simultaneously with an infrared gas analyzer. Characteristic breathing patterns of the insects could be observed; unexpectedly methane was also found to be released.     

Effect of pulsed dye-laser wavelength stabilization on spectral overlap in atmospheric NO fluorescence studies

We introduce an inexpensive application of a Fabry-Perot etalon to control long-term UV-laser line drift in atmospheric NO laser-induced fluorescence (LIF) measurements by monitoring the visible fundamental of a pulsed dye laser. A linear image sensor captures the interference pattern, and the dye grating can be adjusted to maintain a fixed wavelength through an interface with labview software. Results indicate that the laser wavelength can be fixed to an accuracy of +/-0.0001 nm in the dye fundamental and +/-0.00003 nm in the UV beam. Hence the average error in the LIF signal owing to fluctuations in spectral overlap between the laser and the NO absorption transition decreases from ~5 to ~0.05%, which results in improved measurement accuracy.